BRPI0808314B1 - SUPPORTED METAL COMPLEX AND ADDITION POLYMERIZATION PROCESS. - Google Patents

Abstract

supported metal complex, process for preparing a support and supported metal complex addition polymerization process comprising the reaction product of a transition metal complex of a polyvalent heteroaryl donor binder containing at least one ortho-metal aromatic binder group and a Ethylenically or functionalized poly (ethylenically) particulate organic or inorganic solid, method for preparing them and their use as an addition polymerization catalyst.

Description

SUPPORTED METALLIC COMPLEX AND ADD-POLYMERIZATION PROCESS

Background of the Invention [001] The present invention relates to supported transition metal complexes formed from supports functionalized with vinyl or poly (vinyl) which are useful as catalysts for addition polymerization, especially as catalysts for polymerization of olefins. More particularly, the invention relates to rapidly formable supported catalysts comprising a metal complex that is chemically attached or attached to the support via a non-fugitive linker group. The invention also relates to the preparation of such supported compositions, to their use in an olefin polymerization process and to certain functionalized supports, specially adapted for that use.

[002] Many catalysts supported for use in addition polymerizations have been previously described in the state of the art. WO 91/09882 describes a supported catalyst prepared by combining: i) a metal bis (cyclopentadienyl) compound containing at least one ligand capable of reacting with a proton, ii) an activating component comprising a cation capable of donating a proton and a bulky labile anion capable of stabilizing the metallic cation formed as a result of the reaction between the metallic compound and the activating component, and iii). a catalyst support material. Optionally, the supported ion catalyst could be prepolymerized with an olefinic monomer. The support material could also be treated with a hydrolyzable organoadditive, preferably a Group 13 alkyl compound, such as triethyl aluminum. Such

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2/49 supported catalysts do not allow chemically attaching any of the catalyst components to the support material and, consequently, are unsuitable for use in paste polymerizations or other reactions in which solvents or diluents are present and can remove the catalysts from the support.

[003] In US-A-5,427,991, certain catalyst supports are described comprising polyanionic portions consisting of non-coordinating anionic groups chemically linked to cross-linked polymeric core components. It is also known to attach or fix alumoxanes to inert supports. Disadvantageously, the attachment of the cocatalyst to the support results in low productivity catalyst compositions, probably due to the lower activation capacity or activity of immobilized cocatalysts.

[004] Supported metallocene catalysts, where one or more delocalized portions of the metallocene are chemically bonded to particulate organic or inorganic organic materials, including silica, are described in US-A5.399.636, US-A-5.587.439, US-A -6,040,261, WO98 / 09913 and WO98 / -3521. Disadvantageously, the preparation and use of solid functionalized reagents for the synthesis of metallocenes and similar organometallic compounds using synthetic organometallic processes is cost prohibitive and unsuitable for use on an industrial scale. In addition, such processes, which use condensation reactions to bind a catalyst component, also generate one or more by-products that can interfere with further polymerizations. In addition, similar chemicals

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3/49 based on diimine supports and / or functionalized with diimine and used to synthesize donor complexes with Group 3-10 metallic compounds, result in catalysts with inferior catalytic properties, which is supposedly due to the presence of the Lewis base functionality in close proximity to the metallic catalytic center.

[005] In US patent 2002/0083161, certain functionalized particulate supports containing diene or alkaline groups formed by the reaction of silica treated with trialkyl aluminum with the corresponding diene or alkali functionalized alcohols have been described. The compositions were used to prepare supported catalysts for polymerization of olefin by reaction with metal complexes containing substituents capable of reaction with the diene or alkaline functionality of the support. Examples include Group 3-10 metallocene and forced geometry complexes having replaceable binders. Disadvantageously, when the functionalized support comprises one of the donor binders in the active catalyst, interference with the electronic environment of the metal cation or other catalytic species may occur. In addition, if the bond is a single bond to the metal catalytic center, displacement of the solid phase binder by an olefin during polymerization can destroy the bond, resulting in leaching of the catalyst and / or loss of catalytic activity in the presence of liquids , especially of paste thinners.

[006] Certain supports of 2-aminobutadiene substituted in position 4 and bonded to resin, prepared through a Wittig reaction with 2- (N-piperazine) propyl-1-enyl-1-triphenylphosphonium bromide have been described in

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4/49

Tetrahedron, Letters, 38 (40), 7111-7114 (1997). The compositions were found to be useful as resin bound dienes for cycloaddition reactions [4 + 2] in solid phase.

[007] The ability of certain polyvalent amine complexes of Group 4 metals to form orthometallated derivatives via in situ ligand exchange with adjacent aromatic functionality, especially naphthalenyl, was previously described in US-A-2004/0220050. Additional references were generally related to metal complexes based on heteroaryl donor binders centered on polyvalent metal include USP 6.103.657, USP 6.320.005, USP 6.653.417, USP 6.637.660, USP 6.906.160, USP 6.919.407, USP 6.927.256, USP 6.953.764, US-A-2002/0142912, US-A2004 / 0220050, US-A-2004/0005984, EP-A-874.005, EP-A-791.609, WO 2000/20377, WO 2001/30860, WO 2001/46201, WO 2002/24331, WO 2002/38628, WO 2003/040195, WO 2004/94487, WO 2006/20624 and WO 2006/36748.

[008] It would be desirable to provide a supported catalyst for olefin polymerization and a polymerization process using the same one that is capable of producing olefinic polymers under good catalytic efficiencies in which the metal complex is covalently bonded to the support, especially to a particulate organic material. It would also be desirable to provide such a supported catalyst composition devoid of Lewis base groups adjacent or attached to the metal center and which is adapted for use in a paste and / or gas phase polymerization process, and at the same time relatively uninfluenced by the presence of condensed monomer and / or thinners. Finally, it would be desirable if a method were provided to form complexes of

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5/49 supported metal, linked from metal complexes of the

Group 4 that did not involve the preparation of solid compounds containing delocalized π-linked ligand groups or the use of condensation reactions of solid reagents in the synthesis.

Summary of the Invention [009] In one aspect of the present invention, a supported metal complex comprising the reaction product of:

(A) a transition metal complex of a polyvalent heteroaryl donor binder containing at least one ortho-metallized aromatic binder group, and (B) an ethylenically or poly (ethylenically) functionalized organic or inorganic solid.

[010] Under the conditions of the present process, the transition metal complex readily inserts itself into one or more ethylenic unsaturations of the particulate solid, thus creating a covalently bonded bridging group, especially an ethanediyl group, instead of the ortho-metal bond. . Advantageously, the aforementioned process does not result in the concomitant formation of by-products that can interfere with the active catalytic species, as it can occur during a condensation process, and neither does it interfere with the active catalytic species, since the formation of the bond involves the insertion of ethylenic unsaturation in the metal-aryl group bond, creating a bond both to the metal and to the polyvalent binder structure that surrounds the metal. The subsequent activation of the metal complex does not alter the binding to the polyvalent heteroaryl ligand, especially polyvalent heteroaryl amide ligands, even if the metal bond is altered or eliminated due to activation. Beyond

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In addition, the transition metal complex may be in the form of a cationic complex or another active (pre-activated) species before binding to the solid support.

[011] In addition, a supported catalyst composition useful for the polymerization by addition of addition polymerizable monomers, said composition comprising a transition metal complex of a polyvalent heteroaryl donor binder, and a functionalized particulate organic or inorganic solid, is provided. the transition metal complex being covalently bonded to the particulate solid by adding functional ethylene groups of the solid to one or more ortho-metal-aryl bonds of the transition metal complex.

Although the activation of the transition metal complex may occur before or after the formation of the supported catalyst compositions of the invention, in preferred embodiments of the two aspects of the invention mentioned above, the metal complex is activated for polymerization by contact with an activator before combining with the ethylene or poly (ethylenically) functionalized particulate solid support.

More specifically, it is believed that the metal complex comprises a cation, ideally formed by combining the metal complex with an activating cocatalyst before reaction with the ethylenically or poly (ethylenically) functionalized solid support. Consequently, in desirable embodiments, the metal complex in its activated or cationic form retains at least one bond of an orthometallated ligand capable of inserting an ethylene group from the functionalized particulate solid support.

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In another aspect, the invention provides a process for preparing an inorganic oxide support comprising ethylenically unsaturated pendant groups, preferably with vinyl functionality suitable for the preparation of supported metal complexes such as those cited above, said process comprising combining an inorganic oxide material comprising surface hydroxyl groups functionalized with Lewis acid with an aliphatic compound preferably vinyl, ethylenically unsaturated substituted with protonated Lewis base. The resulting supports with vinyl-substituted aliphatic functionality are especially effective in the formation of linked metal complexes with high and sustained catalytic activity. Most desirably, the Lewis base functionality resulting from the formation of the aforementioned linker groups is at least 2, preferably at least 4, and most preferably at least 6 carbons removed from ethylenic unsaturation or pending vinyl functionality.

[014] In yet another aspect, the invention provides an addition polymerization process where one or more addition polymerizable monomers are contacted under addition polymerization conditions with a supported catalyst composition according to the present invention, or preparable according to the present process of the invention.

[015] The supported supports and catalysts of the invention are readily prepared with high yields and efficiencies. It is relevant to note that the catalyst compositions according to the invention demonstrate improved performance as assessed by the catalytic activity and / or apparent density of the product, compared to

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8/49 supported catalyst compositions previously known, especially under paste polymerization conditions. This is believed to result from the ability to bind the metal complex to the surface of inorganic oxide without generating by-products that may interfere with catalytic performance and without the formation of functionality containing electron donor in close proximity to the transition metal.

Detailed description of the invention [016] All references to the Periodic Table of Elements in the present invention refer to the Periodic Table of Elements, published and copyrighted by CRC Press, Inc. 2003. Likewise, any references to a Group or Groups will refer to the Group or Groups in the Periodic Table of Elements using the IUPAC system to number the groups, described in Nomenclature of Inorganic Chemistry: Recommendations 1990, GJLeigh, Editor, Blackwell Scientific Publications (1990). Unless otherwise mentioned, implied from context, or customary in the prior art, all parts and percentages are by weight. For the purposes of American patent practice, the content of any patent, patent application, or publication cited herein is incorporated by reference in its entirety into this patent (or the equivalent American version thereof is incorporated by reference) especially with respect to the description of synthetic techniques, definitions (to a degree not inconsistent with any definitions provided herein) and general knowledge in the state of the art.

[017] The term comprising and its derivatives does not

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9/49 intends to exclude the presence of any additional components, steps or procedures, whether described or not in the present invention. For the avoidance of doubt, all compositions claimed here using the term comprising may include any additive, adjuvant or additional compound, whether polymeric or not, unless otherwise stated. In contrast, the term essentially consists of excluding from the scope of any following quote any other component, step or procedure, with the exception of those that are not essential for operability. The term consisting of excludes any component, step or procedure not specifically described or related. The term or, unless otherwise stated, refers to

members cited in isolation, as well as in any combination. [018] According used here with respect to a compound chemical, unless specifically indicated from another way, the

singular includes all isomeric forms and vice versa (for example, hexane includes all hexane isomers either individually or collectively). The terms compound and complex are used alternatively in the present invention to refer to organic, inorganic and organometallic compounds. The term atom refers to the smallest constituent of an element, regardless of the ionic state, that is, without considering whether or not it is carrying a total or partial charge or if it is connected to another atom.

[019] The term heteroatom refers to an atom other than carbon or hydrogen. Preferred heteroatoms include F,

Cl, Br, N, O, P, B, S, Si, Sb, Al, Se and Ge.

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The term hydrocarbyl refers to univalent substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic or non-cyclic species.

Examples include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkylenyl, aryl and alkynyl groups.

Substituted hydrocarbyl refers to a hydrocarbyl group that is substituted with one or more non-hydrocarbyl substituent groups. The term heterocarbyl refers to groups containing one or more carbon atoms and one or more hetero atoms and no hydrogen atoms. The bond between the carbon atom and any hetero atom, as well as the bonds between any two hetero atoms, can be a single or multiple covalent bond, or a coordinating bond or other dative bond.

Examples include trichloromethyl, pefluorophenyl, cyano and isocyanate groups. The terms hydrocarbyl containing heteroatom or heterohydrocarbyl refer to univalent groups in which at least one atom other than hydrogen or carbon is present together with one or more carbon atoms and one or more hydrogen atoms. Thus, an alkyl group substituted with a halo, heterocycloalkyl, heterocycloalkyl group substituted with aryl, heteroaryl, alkyl, heteroaryl substituted with alkyl, alkoxy, aryloxy, dihydrocarbilboril, dihydrocarbilfosfino, dihydrocarbilamino, trihydrocarbilsilila, hydrocarbelo or hydrocarbyl is hydrocarbyl. Examples of suitable heteroalkyl groups include chloromethyl groups,

2-cyanoethyl, hydroxymethyl, benzoylmethyl, (2pyridyl) methyl, chlorobenzyl, and trifluoromethyl.

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11/49 [021] As used here, the term aromatic refers to a polyatomic, cyclic, conjugated ring system containing π-electrons (4δ + 2), where δ is an integer equal to or greater than 1. The fused term as used herein with respect to a ring system containing two or more cyclic polyatomic rings, it means that with respect to at least two rings of the same, at least one pair of adjacent atoms is included in the two rings. The term aryl refers to a monovalent aromatic substituent that can be a single aromatic ring or multiple aromatic rings that are fused together, covalently linked, or linked to a common group such as a methylene or ethylene moiety. Examples of aromatic ring (s) include phenyl, naphthyl, anthracenyl, and biphenyl, among others.

[022] Substituted aryl refers to an aryl group in which one or more hydrogen atoms attached to any carbon is substituted with one or more functional groups such as alkyl, alkenyl, substituted alkyl, substituted alkenyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halo, haloalkyl (e.g. CF ₃ ), hydroxy, amino, phosphide, alkoxy, amino, uncle, nitro, and both saturated and unsaturated hydrocarbyl groups, including those which are fused with aromatic ring (s) ), covalently linked or attached to a common group such as methylene or ethylene moiety. The common linking group can also be carbonyl as in benzophenone groups, oxygen as in diphenyl ether groups or nitrogen as in diphenylamine groups.

[023] Ethylenic unsaturation or ethylenic group refers to adjacent aliphatic carbon atoms, joined

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12/49 _Λ 2 by double bonds (electronic non-aromatic sp hybridization), preferably of the formula: -CR * = CR * -, or CR * = CR * ₂ , where R * regardless of each occurrence is hydrogen, halo, nitrile, hydrocarbyl or substituted hydrocarbyl containing up to 20 atoms not containing hydrogen. The percent ethylenic unsaturation, as used here, is calculated based on the total carbon-carbon bond content of the polymer. The term pendant refers to groups or substituents attached to substituted secondary or tertiary carbons of the polymer. The term terminal refers to groups or substituents attached to a primary carbon of the polymer. Terminal ethylenic unsaturation is alternatively referred to here as vinyl (vinyl) unsaturation.

[024] The term polymer, as used herein, refers to a macromolecular compound comprising multiple repeat units and a molecular weight of at least 100, preferably at least 1000. Preferably, at least one repeat unit occurs, consecutive or non-consecutive, 6 or more times, more preferably 20 or more times, on average. Molecules containing less than 6 of these repeating units on average are referred to herein as oligomers. The term includes homopolymers, copolymers, terpolymers, interpolymers and so on. The term interpolymer is used interchangeably with the term copolymer to refer to polymers that incorporate, in the polymerized form, at least two different repeating units, generally obtained from separate copolymerizable monomers. The least prevalent monomer in the resulting copolymer or interpolymer is generally referred to as the term comonomer.

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13/49 [025] The term fugitive as used here, refers to binders in a metal complex that are subject to losses under conditions of activation or polymerization. In particular, fugitive ligands are leaving groups that form an active catalytic species, especially a cation, by reacting with a Lewis acid. Surprisingly, it was found that by using the unique combination of supported catalyst compositions or supports as specified herein, activated transition metal catalysts can be employed to produce olefinic polymers with extremely high catalytic efficiencies. Preferably, the catalysts achieve efficiencies of at least 1 x 10 ⁵ g polymer / g transition metal, more preferably at least 1x10 ⁶ g polymer / g transition metal. In addition, these supported catalysts are highly immune to leaching under typical process conditions employed in gas phase polymerization or, especially, in paste and the binding ligand formed by the insertion of ethylenic unsaturation in the ortho-metallized ligand is not fugitive.

[026] Additional benefits in using the supported catalysts of the present invention in polymerization processes include the fact that the formation of polymer deposits on the reactor walls and other moving parts of the reactor (due to catalyst leaching from the support) is avoided , thus obtaining polymers with improved bulk density in particle-forming polymerization processes with improved reliability and operability. According to the present invention, improved apparent densities for homopolymers and interpolymers containing

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14/49 ethylene are apparent densities of at least 0.20 g / cm ³ and preferably at least 0.25 g / cm ³ .

[027] Particulate supports suitable for use in the present invention include inorganic oxide supports, especially silicas, aluminins, aluminosilicates, aluminophosphates, clays, highly porous titanias, and mixtures thereof. Suitable organic solids include natural and synthetic resins, including polyethylene, polypropylene, polyesters, polyvinyl alcohols, and polyvinylaromatic polymers. Preferred particulate supports are inorganic oxides, especially alumina and silica. The most preferred support material is silica. The support material can be granular, agglomerated, pelletized or any other physical form. Preferred substrates have a surface area determined by nitrogen porosimetry using the BET method from 10 to 1000 m ² / g, and preferably from 100 to 600 m ² / g. The pore volume of the support, as determined by nitrogen adsorption, is advantageously between 0.1 and 3 cm ³ / g, preferably between 0.2 to 2 cm ³ / g. The average particle size is not critical, although it is typically 0.5 to 500 pm, preferably 1 to 150 pm.

[028] Inorganic oxides, especially silica, alumina and aluminosilicates are known to have inherently small amounts of hydroxyl functionality linked to the atomic matrix. When used in the preparation of the supported supports and metal complexes of the present invention, these materials are preferably first subjected to a thermal treatment, followed by treatment with a Lewis acid to reduce the surface hydroxyl content of them.

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15/49 to less than 10 mmol / g, more preferably to less than 1.0 mmol / g, most preferably to less than 0.8 mmol / g. Typical heat treatments (calcination) are carried out at a temperature of 150 to 900 ^o C, preferably from 200 to 850 ^o C for a period of 10 minutes to 50 hours. Lewis acid treatments include contacting Lewis acid alkylating agents, such as trihydrocarbyl aluminum compounds, trihydrocarbyl chlorosilane compounds, trihydrocarbylalkoxysilane compounds, or similar agents. Residual hydroxyl functionality can be detected using the Fourier Transform Infrared Spectroscopy (DRIFTS IR) as described in Fourier Transform Infrared Spectroscopy, P. Griffiths & J.de Haseth, 83 Chemical Analysis, Wiley Interscience (1986), p. 544.

[029] Inorganic oxide can be non-functionalized, except for the conversion of surface hydroxyl groups, as previously described. The inorganic oxide can also be functionalized by treatment with a silane, hydrocarbiloxysilane, chlorosilane, borane or other functionalizing agent to bind to the same pending functionality for further modification purposes, if desired. Suitable functionalizing agents are compounds that react with available surface hydroxyl groups of the inorganic oxide or that react with the metal or metalloid atoms of the inorganic oxide matrix. Examples of suitable functionalizing agents include phenylsilane, diphenylsilane, methylphenylsilane, dimethylsilane, diethylsilane, detoxysilane, and chlorodimethylsilane, etc. Techniques for forming such inorganic oxide compounds have previously been

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16/49 described in US-A-3,687,920 and US-A-3,879,368.

[030] In a preferred embodiment, the inorganic oxide is non-functionalized, except for the presence of groups with Lewis acid functionality capable of reaction as described herein. Preferably, the Lewis acid groups are incorporated through the reaction between tri (C 1-4 alkyl) aluminum compounds, especially trimethyl aluminum, with hydroxyl portions of the inorganic oxide surface. The reaction is caused by contacting the tri (C14 alkyl) aluminum compounds with the inorganic oxide material, optionally in the presence of a hydrocarbon diluent, still optionally in the presence of a base adjuvant, such as C1-4 trialkylamine. The reaction is conducted at a temperature of 0 to 110 ^o C, preferably 20 to 50 ^o C. Generally, an excess of Lewis acid compound is employed based on the hydroxyl content of the particulate solid. Preferred Lewis acid: particulate solid ratios are from 1 to 2500 mmol / g. As a result of the aforementioned reaction, the residual hydroxyl functionality of the inorganic oxide is reduced or further reduced to the desired, most desired, or most desired levels previously mentioned. Preferably in the preparation of the functionalized support materials of the present invention, a calcined silica is employed, having an initial residual hydroxyl content (ie, pre-functionalized) of less than 1.0 mmol / g, being employed from 1 to 20 mmol of Lewis acid functionalizing agent / g silica. The molar ratio of the base adjuvant, if any, used for the Lewis acid functionalizing agent is generally 0.01 to 2.0: 1. The unreacted functionalizing agent is preferably removed from the

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17/49 surface of the inorganic oxide, for example, by washing with a liquid hydrocarbon, and the support is completely dried before use in the preparation of the functionalized supports of the present invention.

[031] The functionalized support, supported metal complex or supported catalyst composition can also be treated with an aluminum component selected from an alumoxane or an alumoxane modified with trialkylaluminium, according to techniques known in the prior art to remove or sweep catalyst poisons. Preferably, the aluminum component is selected from the group consisting of aluminoxanes and alumoxane compounds modified with tri (hydrocarbyl C _1-4 ) aluminum. The most preferred aluminum components are metallumoxane, metallumoxane modified with triisobutylaluminum, and mixtures thereof. The sweeper can also be added to the polymerization mixture in a reactor in which the supported catalyst composition of the present invention is employed. Alternatively, alumoxane can serve as part or all of the activating cocatalyst in the resulting supported activated catalyst composition.

[032] Alumoxanes (also called aluminoxanes) are oligomeric or polymeric oxyalumin compounds containing chains of alternating atoms of aluminum and oxygen, through which aluminum carries a substituent, preferably an alkyl group. The alumoxane structure is believed to be represented by the following general formulas (-Al (R) -O) m, for a cyclic alumoxane, and R2Al-O (Al (R) -O) m-AIR2, for a linear compound , where R is C1-4 alkyl and m is an integer ranging from 1 to 50, preferably

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18/49 at least 4. Alumoxanes are typically the reaction products of water and an alkyl aluminum, which in addition to an alkyl group may contain halide or alkoxide groups. Reacting various alkyl aluminum compounds, such as, for example, trimethyl aluminum and triisobutyl aluminum with water produces so-called modified or mixed alumoxanes. Preferred alumoxanes are methylalumoxane and methylalumoxane modified with secondary amounts of C _2-4 alkyl groups, especially isobutyl groups. Alumoxanes generally contain amounts ranging from minor to substantial starting aluminum alkyl compounds.

[033] Specific techniques for the preparation of alumoxane-type compounds by contacting an alkyl aluminum compound with an inorganic salt containing water of crystallization are described in US-A-4,542,119.

In a particularly preferred embodiment, an alkyl aluminum compound is contacted with a substance containing regenerable water such as alumina, silica or another hydrated substance. This is described in that the alumoxane can be incorporated into the support by reacting a hydrated silica or alumina material, which has been optionally functionalized with silane, siloxane, hydrocarbiloxysilane or chlorosilane groups, with a tri (C1-10 alkyl) aluminum compound of according to acquaintances.

The conversion of hydroxyl groups on the surface of the particulate support carried out through the acid functionality reaction of

Lewis, especially alkyl aluminum functionality, with an ethylenically unsaturated compound containing

Protonated Lewis, especially a compound functionalized with hydroxyl, thiol,

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19/49 hydrocarbilamine, di (hydrocarbyl) amine, hydrocarbilphosphine or di (hydrocarbyl) phosphine containing vinyl functionality.

Especially preferred reagents are alcohols, thiols, hydrocarbilamines, di (hydrocarbyl) amines, hydrocarbylphosphines or primary aliphatic ethylenically or polyethylenically unsaturated phosphines containing from to 20 carbons, especially those containing terminal ethyl unsaturation.

[035]

The addition of oxyalkyl diene functionality to silica treated with alkyl aluminum

2002/0082161. The addition of polymeric substrates was previously described in US-Aminoalkyl diene functionality a was previously described in

Tetrahedron Letters, 38 (40), 7111-7114 (1997). Any of these techniques or variations thereof can be employed in the preparation of poly (ethylenic) unsaturation in bonds employed in accordance with the present invention. However, preferred reagents are substituted aliphatic V-alcohols, having from 5 to 20 carbons, preferably from 7 to 20 carbons. Examples include V-octen-1-ol, V-nonen-1-ol, V-decen-1-ol, V-undecen1-ol, V-dodecen-1-ol and V-octadecen-1-ol.

[036] Transition metal complexes suitable for use in the present invention include any transition metal complex containing a bond of the transition metal to an adjacent aromatic ring in an ortho position relative to another bond external to the aryl ligand, and in which a group ethylene can be inserted. Examples include, but are not limited to, Group 4 metal derivatives, especially hafnium derivatives, of hydrocarbilamine-substituted heteroaryl compounds corresponding to the formula:

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Where :

[037] R ¹¹ is a hydrocarbyl or heterohydrocarbyl group containing up to 30 atoms not containing hydrogen;

[038] T ¹ is a divalent bridged group of 1 to 41 atoms other than hydrogen, preferably 1 to 20 atoms other than hydrogen and most preferably a methylene or silane group substituted with C1-20 mono or dihydrocarbyl;

[039] R ¹² is a substituted heteroaryl group containing Lewis base functionality of up to 20 atoms, not containing hydrogen, and comprising an aryl or heteroaryl group or a divalent derivative thereof, especially a substituted or imidazolyl substituted pyridinyl group or a divalent derivative the same;

[040] M ¹ is a Group 4 metal, preferably zirconium or hafnium, most preferably hafnium;

[041] M ¹ is a Group 4 metal, preferably zirconium or hafnium, most preferably hafnium;

[042] X ¹ is an anionic, neutral or dianionic linking group;

[043] x 'is a number from 0 to 5 indicating the number of such groups X ¹ ; and [044] electron donor bonds and interactions are represented by lines and arrows respectively, and ortho-metal bonds between R ¹² and M ¹ and optionally between R ¹¹ and M ¹ , are indicated by dotted lines.

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21/49 [045]

Preferred metal complexes correspond to the formula:

defined,

cycloalkyl, heteroalkyl group,

as previously hydrogen, halo or alkyl, heterocycloalkyl, aryl or silyl of up to 20 atoms not counting hydrogen, or groups R ¹³ , R ¹⁴ or

Adjacent R ¹⁵ can be joined, thus forming fused ring derivatives,

R ¹⁶ is an aryl group or substituted aryl group, electron pair donor bonds and interactions are represented by lines and arrows respectively, and [051] ortho-metal ligand interactions between M ¹ and R ¹⁶ are indicated by dotted lines.

[052] Most preferred examples of metal complexes correspond to the formula:

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[053] where [054] Μ ^1, X ¹ and x 'are as previously defined, [055] R ^13, R ¹⁴ and R ¹⁵ are as previously defined, preferably R ^13, R ¹⁴ and R ¹⁵ are hydrogen or alkyl CI_ ₄ , and [056] R ¹⁶ is a C6-2o <aryl, most preferably 2naphthalenyl, also linked to M ¹ via an orthometallated bond;

[057] R ^a regardless of each occurrence is C1-4 alkyl, and a is 1-5, most preferably R ^a in two positions ortho to hydrogen is isopropyl or t-butyl;

[058] R ¹⁷ and R ¹⁸ independently of each occurrence are hydrogen, halogen or C1-2 alkyl or aryl group <most preferably one of R ¹⁷ and R ¹⁸ is hydrogen and the other is a C6-2o aryl group <especially group 2- isopropyl, phenyl or a fused polycyclic aryl, most preferably an anthracenyl group, and [059] electron pair donor bonds and interactions are represented by lines and arrows, respectively, and ortho-metal ligand interactions are indicated by dotted lines.

[060] Highly preferred ortho-metallized, polyfunctional amine donor metal complexes for use in the present invention correspond to the formula:

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alkyl aralkyl

C1-4 methyl;

in each dimethyl starch, occurrence X ¹ is

Where

preferably [062] R ^c , R ^f and R ^g regardless of each occurrence are halogen, C1-20 alkyl <or C6-20 aryl or two adjacent R ' ^c , R ^f or R ^{g groups} are joined to form a ring, c integer from 1 to 4, eg, independently, are integers from 1-5;

R ^h regardless of hydrogen or C1-6 alkyl;

electron pair donor connections and interactions are represented by lines and arrows respectively and ortho-metalized ligand interactions are indicated by dotted lines.

[065] The most highly preferred examples of such polyvalent ortho-metalized amine donor complexes are composed of the formulas:

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24/49

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25/49 where:

[066] d, R is hydrogen or C _1-6 alkyl, the most

preferably ethyl;

[067] R ⁱ is methyl or isopropyl; [068] R ^j is hydrogen, C _1-6 alkyl or cycloalkyl, or

two adjacent R ⁶ groups together form a fused aromatic ring, preferably two R ⁶ groups together on the 5 ring

members form a benzo-substituent; [069] R ^x is C _1-4 alkyl or cycloalkyl, preferably methyl, isopropyl, t-butyl or cyclohexyl; [070] X ¹ in each occurrence is halide, N, N-dimethyl starch,

or C _1-4 alkyl, preferably methyl,

[071] electron pair donor bonds and interactions

are represented by lines and arrows respectively, and ortho-metalized ligand interactions are indicated by dotted lines.

[072] Examples of previously ortho-metallized complexes cited include: [073] Dimethyl [N- [2,6-bis (1-methylethyl) phenyl] a- [2- (1-

methylethyl) phenyl] -6- (1,2-naphthalendiyl-KC ^{2 *} ) -21 2 pyridinomethanaminate (2) -KN, kN] hafnium,

[074] Di (n-butyl) [N-2,6-bis (1-methylethyl) phenyl] a- [2- (1-

methylethyl) phenyl] -6- (1,2-naphthalenyl-KC ² ) -21 2 pyridinomethanaminate (2) -KN, kN] hafnium,

[075] Dimethyl [N- [2,6-bis (1-methylethyl) phenyl] a- [2,6-bis (1-

methylethyl) phenyl] -6- (1,2-naphthalendiyl-KC ² ) -21 2 pyridinomethanaminate (2) -KN, kN] hafnium,

[076] Di (n-butyl) [N-2,6-bis (1-methylethyl) phenyl] -a- [077] [2,6-bis (1-methylethyl) phenyl] -6- (1,2-naphthalenyl-K-

12

C) -2-pyridinomethanaminate (2) -KN, kN] hafnium,

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26/49

[078] Dimethyl [N-2,6-bis (1-methylethyl) phenyl] -a- [079] [2,6-bis (1-methylethyl) phenyl] -5- (2-ethylbenzofuran-3- il-KC ⁴ ) -2- (Ν'-methyl) imidazol-2-yl) methanaminate (2) -κΝ ¹ ,

_ζ κΝ] hafnio,

[080] Di (n-butyl) [Ν-2,6-bis (1-methylethyl) phenyl] -a- [081] [2,6-di (1-methylethyl) phenyl] -5- (2-ethylbenzofuran-3- il-κ-Ο ⁴ ) -2- (Ν'-methyl) imidazol-2-yl) methanaminate (2) - κΝ ¹ , κΝ ² ] hafnium,

[082] Di (methyl) [N- [2,4,6-tris (1-methylethyl) phenyl] -a [2,6di (1-methylethyl) phenyl-5- (2-ethylbenzofuran-3-yl-KC ⁴ ) - 2- (Ν'1 2 methyl) imidazol-2-yl) methanaminate (2) -KN, κΝ] hafnium; and [083] Di- (n-butyl) [N- [2,4,6-tris (1-methylethyl) phenyl] -a [2,6-bis ((1-methylethyl) phenyl] -6- (1 , 2-naphthalenyl-KC ² ) -2pyridinomethanaminate (2) -KN, κΝ] hafnium.

[084] The metal complexes supported according to the invention can be activated in different ways to produce the catalyst compounds having a vague coordination site that will coordinate, insert and polymerize addition-curable monomers, especially olefin (s). Both activated and inactivated or neutral metal complexes are included in the present invention. For the purposes of this report and the appended claims, the term activator or cocatalyst is defined as any compound or component or method that can convert any of the catalyst compounds of the invention into addition polymerization catalysts. Non-restrictive examples of suitable activators include Lewis acids, non-coordinating ionic activators, ionizing activators, organometallic compounds, and combinations of the aforementioned substances that can convert a catalyst compound

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27/49 neutral in a catalytically active species.

[085]

It is believed, without being linked to this fact, that in one embodiment of the invention, catalytic activation may involve the formation of a cationic species, partially cationic or zwiterionic, through proton transfer, oxidation, or other appropriate activation process.

It should be understood that the present invention is operable and totally possible, regardless of whether such a cationic, partially cationic or identifiable zwitterionic species occurs or not during the activation process, also alternatively referred to as the ionization process or ionic activation process.

The corresponding cationic derivatives of the metal complexes illustrated and previously mentioned have a positive charge located on the transition metal, an X ¹ group attached to the transition metal and an associated, preferably non-coordinating, anion derived from the activator through the abstraction of an X ¹ group. , oxidation of the transition metal or dissociation of the activator.

A suitable class of organometallic activator or cocatalyst is an alumoxane, also called alkylaluminoxane.

Alumoxanes are acid activators of

Lewis well known for use with metallocene-type catalyst compounds to prepare addition polymerization catalysts. There are a variety of methods for preparing modified alumoxanes and alumoxanes, the non-restrictive examples of which are described in US patents

4,665,208,

4,952,540,

5,091,352,

5,206,199,

5,204,419,

4,924,018, .908,463,

5,329,032,

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28/49

5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656; publications European EP-A-561476, EP-A-279586 and EP-A-594218 and publication

PCT WQO 94/10180. Preferred alumoxanes are tri (C _3-6 alkyl) modified methylalumoxane, especially tri (isobutyl) modified metalumoxane, available on the market as MMAO-3A or tri (noctil) aluminum modified metallumoxane, available on the market as MMAO- 12, by Akzo Nobel, Inc.

[088] The use of alumoxane (s) or modified alumoxane (s) as an activator or as a tertiary component of the process of the invention is part of the scope of the present invention. That is, the compound can be used alone or in combination with other neutral or ionic activators, such as tri (alkyl) ammonium tetracis (pentafluorophenyl) borate compounds, trisperfluoroaryl compounds, polyhalogenated heteroborane anions (WO 98/43983) , and their combinations. When used as a tertiary component, the amount of alumoxane used is generally less than that needed to effectively activate the metal complex when used alone. In this embodiment, it is believed, without being linked to such fact, that alumoxane does not contribute significantly to the effective formation or catalytic activation. Despite the above, it is understood that some participation of alumoxane in the activation process is not necessarily excluded.

[089] Ionizing cocatalysts may contain an active proton, or some other cation associated with, but not coordinated with, or only weakly coordinated with, an anion of the ionizing compound. Such compounds are described in

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29/49 European publications EP-A-570982, EP-A-520732, EP-A-495375, EP-A-500944, EP-A-277003 and EP-A-277004 and American patents Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124. Among the previously mentioned activators the preferred ones are salts containing ammonium cation, especially those containing trihydrocarbyl-substituted ammonium cations containing one or two C _10-40 alkyl groups, especially methylbis (octadecyl) ammonium and methylbis (tetradecyl) ammonium cations and an anion non-coordinating, especially a tetracis (perfluoro) arylborate anion, especially tetracis (pentafluorophenyl) borate. It is also understood that the cation may comprise a mixture of hydrocarbyl groups of different lengths. For example, the protonated ammonium cation derived from commercially available long chain amine comprising a mixture of C14 alkyl groups,

C ₁₆ or C18 ^and one methyl group . Such amines they're from Chemtura Corp., by having O commercial name Kemamine ™ T9701 and Akzo Nobel with the name commercial of Armeen ™ M2HT. The most preferred

ammonium salt activator is tetracis (pentafluorophenyl) methyldi (C1420 alkyl) ammonium borate.

[090] Activation methods using ionizing ionic compounds that do not contain an active proton, but which are capable of forming active catalyst compositions through oxidative or other processes, especially ferrocenic salts from the aforementioned non-coordinating anions, are also intended for use in the present invention and are described in EP-A-426637, EP-A-573403 and US-A-5,387,568.

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30/49 [091] A class of cocatalysts comprising non-coordinating anions generically designated as expanded anions, also described in US-A-6,395,671, can be suitably employed to activate the metal complexes of the present invention for olefin polymerization. Generally, these cocatalysts (illustrated by those with imidazolid, substituted imidazolid, imidazolinide, substituted imidazolinide, benzimidazolid, or substituted benzimidazolid anions) can be illustrated as follows:

Where:

[092] A * ⁺ is a cation, especially a proton-containing cation, and preferably a trihydrocarbyl ammonium cation containing one or two C10-40 alkyl groups, especially a methyldi (C14-20 alkyl) ammonium cation.

[093] R ⁴ , regardless of each occurrence, is hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silyl hydrocarbyl, or silyl (including mono, di and tri (hydrocarbyl) silyl) of up to 30 atoms not containing hydrogen, preferably alkyl C1-20, and J * 'is tris (pentafluorophenyl) borane or tris (pentafluorophenyl) aluminum).

[094] Examples of these catalytic activators include trihydrocarbylammonium salts, especially salts of

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31/49 methyldi (C ₁₄ - ₂ o alkyl) ammonium of:

[095] bis (tris (pentafluorophenyl) borane) imidazolid, [096] bis (tris (pentafluorophenyl) borane) -2undecylimidazolid, [097] bis (tris (pentafluorophenyl) borane) -2heptadecylimidazolide, [098] bis borane) -4.5 bis (undecyl) imidazolid, bis (tris (pentafluorophenyl) borane) -

4.5- bis (heptadecyl) imidazolid, [099] bis (tris (pentafluorophenyl) borane) imidazolinide, [100] bis (tris (pentafluorophenyl) borane) -2undecylimidazolinide, bis (tris (pentafluorophenyl) borane) -2heptadil pentafluorophenyl) borane) -

4.5- bis (undecyl) imidazolinide, bis (tris (pentafluorophenyl) borane) -4,5bis (heptadecyl) imidazolinide, [101] bis (tris (pentafluorophenyl) borane) -5,6dimethylbenzimidazolide, [102] bis (tris (pentafluoren) borane) -5,6- bis (undecyl) benzimidazolid, bis (tris (pentafluorophenyl) aluminum) imidazolid, [103] bis (tris (pentafluorophenyl) aluminum) -2undecylimidazolid, [104] bis (tris (pentafluorophenyl) alumina, humanized) , bis (tris (pentafluorophenyl) aluminum) -

4.5- bis (undecyl) imidazolid, [105] bis (tris (pentafluorophenyl) aluminum) -4,5- bis (heptadecyl) imidazolid, [106] bis (tris (pentafluorophenyl) aluminum) imidazolinide, [107] bis (tris ( pentafluorophenyl) aluminum) -2

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32/49 aluminum undecylimidazolinide, bis (tris (pentafluorophenyl)) -2heptadecylimidazolinide, bis (tris (pentafluorophenyl)

4,5-bis (undecyl) imidazolinide, [108] bis (tris (pentafluorophenyl) aluminum) -4,5-bis (heptadecyl) imidazolinide, [109] bis (tris (pentafluorophenyl) aluminum) -5,6dimethylbenzimidazolid, and [ 110] bis (tris (pentafluorophenyl) aluminum) -5,6- bis (undecyl) benzimidazolid.

[111] Other activators include those described in PCT publication WO 98/07515 such as tris (2,2 ', 2nonafluorobiphenyl) fluoroaluminate. Combinations of activators are also provided by the invention, for example, alumoxanes and ionizing activators in combinations, see for example EP-A0 573120, PCT publications WO 94/07928 and WO 95/14044 and US patents Nos. 5,153,157 and 5,453,410. WO 98/09996 describes catalyst activating compounds with perchlorates, periodates and iodates, including their hydrates. WO 99/18135 describes the use of organoboroaluminators. EP-A781299 describes the use of a silyl salt in combination with a compatible non-coordinating anion. Other activators and methods for activating a catalyst compound are described, for example, in U.S. patents 5,849,852, 5,859,653,

5,869,723, EP-A-615981 and PCT publication WO 98/32775.

[112] It is also within the scope of the present invention that the supported metal complex compositions described can be combined with more than one of the activators or activation methods described above. The molar ratio of the activating component (s) to the metal complex in the catalyst compositions of the invention is suitably situated

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33/49 in the range of 0.3: 1 to 2000: 1, preferably from 1: 1 to 800: 1, and most preferably from 1: 1 to 500: 1. When the activator is an ionizing activator, such as those based on the tetracis anion (pentafluorophenyl) boron or strong Lewis acid trispentafluorophenylboro, the molar ratio of the metal or metalloid of the activating component to the metal complex is preferably in the range of 0, 3: 1 to 3: 1.

[113] Tertiary Components [114] In addition to the supported activated transition metal complex, it is envisaged that certain tertiary components or mixtures thereof can be incorporated into the supported catalyst composition or polymerization mixture, to obtain improved catalytic performance or other benefit. Examples of such tertiary components include sweepers designed to react with contaminants in the reaction mixture to avoid deactivating the catalyst. Appropriate tertiary components can also activate or assist in the activation of one or more of the metal complexes employed in the catalyst composition or act as chain transfer agents. As previously noted, such a tertiary component may also be a component of the supported bound metal complex composition.

Examples include acids from

Lewis, such as trialkyl aluminum compounds, dialkyl zinc compounds, dialkyl aluminum alkoxides, dialkyl aluminum aryloxides,

Dialkyl aluminum N, N-dialkylamides,

N, N-dialkylamides of di (trialkylsilyl) aluminum, N, N di (trialkylsilyl) amides of dialkyl aluminum, alkyl aluminum alkoxides, (di (N, N-dialkylamides) of alkyl aluminum,

N, N-dialkylamides of tri (alkyl) silyl aluminum, N, N Petition 870180145510, of 10/29/2018, p. 38/57

34/49 di (trialkylsilyl) alkyl aluminum amides, alkyl aluminum diaryloxides, alkyl aluminum bis (amides) such as bis (ethyl aluminum) -1-phenylene-2- (phenyl) starch μbis (diphenylamide) and / or alumoxanes ; as well as Lewis bases, such as organic ether, polyether, amine, and polyamine compounds. Many of the previously mentioned compounds and their use in polymerizations are described in U.S. Pat. 5,712,352 and 5,763,543 and in WO 96/08520. Preferred examples of the aforementioned tertiary components include trialkyl aluminum compounds, dialkyl aluminum aryloxides, alkyl aluminum diaryloxides, dialkyl aluminum amides, alkyl aluminum diamides, tri (hydrocarbylsilyl) dialkyl aluminum, bis (tri (hydrocarbylsilyl) amides), alkoxyalanes, aluminum and aluminum. modified alumoxanes.

Highly preferred tertiary components are alumoxanes, modified alumoxanes or compounds corresponding to the formula R ^and 2Al (OR) ^f ) or R ^and 2Al (NR ^g 2) where R ^e is C1-20 alkyl, R ^f regardless of each occurrence is C6- 20, preferably phenyl or 2,6di-t-butyl-4-methylphenyl, and R ^g is C1-4 alkyl or tri (C14 alkyl; silyl, preferably trimethylsilyl.

Most highly preferred tertiary components include methyl (isobutylaluminum) modified methylalumoxane, di (n-octyl) 2,6-dit-butyl-4-methylphenoxide and di (2-methylpropyl) N, Nbis (trimethylsilyl) amide aluminum.

[116] Another example of an appropriate tertiary component is a hydroxycarboxylate metal salt, that is any hydroxy-substituted mono, di or tri-carboxylic acid salt, where the metal portion is a cationic derivative of a metal from Groups 1-13 of the Periodic Table of Elements. That

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35/49 compound can be used to improve the morphology of the polymer especially in a gas phase polymerization. Non-restrictive examples include saturated, unsaturated, aliphatic, aromatic, cyclic saturated, substituted carboxylic acid salts, where the carboxylate linker has from one to three hydroxy substituents and from 1 to 24 carbon atoms. Examples include hydroxyacetate, hydroxypropionate, hydroxybutyrate, hydroxyvalerate, hydroxypivalate, hydroxycaprilate, hydroxyheptanate, hydroxypellargonate, hydroxyundecanoate, hydroxyoleate, hydroxyoctoate, hydroxylmitate, hydroxy-arythrate, hydroxyarcharate, hydroxyarcharate, hydroxyarcharate, hydroxyarcharate, hydroxyarcharate, hydroxyarcharate, hydroxyarcharate, hydroxyarcharate, hydroxyarcharate, hydroxyarcharate, hydroxyarcharate.

Non-restrictive examples of the metal portion include a metal selected from the group consisting of Al, Mg, Ca, Sr, Sn, Ti, V, Ba, Zn, Cd, Hg, Mn, and, Co, Ni, Pd, Li and Na. Preferred metal salts are zinc salts.

[117] In one embodiment, the hydroxycarboxylate metal salt is represented by the following general formula:

M (Q) _x (OOCR) _y , where

M is a metal from Groups 1 to 16 and the series of Lanthanides and Actinides, preferably from Groups 1 to 7 and from 12 to 16, more preferably from Groups 3 to 7 and from 12 to 14, even more preferably from Group 12 and the more preferably

Zn;

Q is a halogen, hydrogen, hydroxide, or an alkyl, alkoxy, aryloxy, siloxy, silane, sulfonate or siloxane group of up to 20 atoms not containing hydrogen;

R is a hydrocarbyl radical having 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, and

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36/49 optionally substituted with one or more hydroxy, alkoxy, N, N-dihydrocarbilamino, or halo groups, provided that in one instance R is replaced with a hydroxy group or N, Ndihydrocarbilamino, preferably a hydroxy group that is coordinated with the metal, M through electrons not shared by them;

x is an integer from 0 to 3;

y is an integer from 1 to 4.

[118] In a preferred embodiment, M is Zn, x is 0 and y is 2.

[119] Preferred examples of hydroxycarboxylate metal salts include compounds of the formulas:

where hydrogen,

mdependent emente halogen or alkyl CI_ _6.

Other additives can \ J

catalyst compositions or employed simultaneously in the polymerization reaction for one or more useful purposes. Examples of additives that are known in the art include metal salts of fatty acids, such as aluminum, zinc, calcium, titanium or magnesium mono, di and tristearates, octoates, oleates and cyclohexylbutyrates. Examples of such additives include Aluminum Stearate # 18, Aluminum Stearate # 22, Aluminum Stearate # 132 and Aluminum Stearate

EA Food Grade Aluminum, all from Chemtura Corp. 0 use

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37/49 of such additives in a catalyst composition is described in

UA-A-6,306,984.

[121] Suitable additional additives include antistatic agents such as fatty amines, for example, ethoxylated stearylamine AS 990, zinc additive AS 990/2, a mixture of ethoxylated stearylamine and zinc stearate, or AS 990/3, a mixture of stearylamine ethoxylated, zinc stearate, and octadecyl-3,5-di-ter-butyl-4 hydroxyhydrocinamate, also from Chemtura Corp.

[122] The tertiary compounds described above can be combined with the support, if desired, or added to the reaction mixture as separate components. In a highly desirable manner, the tertiary component or components are present in a supported form, for example, deposited on, contacted with or incorporated into the supported linked catalyst compositions of the present invention.

[123]

The supported catalyst of the present invention generally comprises from 0.001 to 10 mmol of transition metal complex per gram of particulate solid, preferably from 0.01 to 1 mmol / g. Under higher loads of transition metal complex, the support becomes too expensive. In very low amounts, the catalyst efficiency of the resulting supported catalyst becomes unacceptable.

[124] The support of the present invention can be stored or shipped under inert conditions in the form it is in or converted to paste with an inert diluent, such as alkane or aromatic hydrocarbons. If not yet in cationic form, it can be used to generate the supported supported catalyst through contact with a cocatalyst or compound

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38/49 appropriate activator optionally in the presence of a liquid diluent.

[125]

Generally, the ratio of moles of activating compound to moles of transition metal compound in the supported catalyst is 0.5: 1 to 1000: 1, preferably 0.8: 1 to

500: 1, and most preferably

1: 1 to 100: 1. Certain cation-forming initiators containing non-coordinating anions can be used at much lower levels, specifically 0.5: 1 for

100: 1, preferably from 0.8: 1 to 10: 1 and most preferably from 1: 1 to 2: 1 based on the metal complex. At very low ratios, the supported catalyst will not be very active, while at too high ratios the due to the amounts of the catalyst cost will be too high for relatively large activator compounds used.

gift

The supported metal complex and / or catalyst of the invention can be prepared by combining the particulate solid support, the transition metal complex and the optional activating compound, in any order. In one embodiment, the supported inactivated transition metal complex is treated with a solution of the activating compound by combining the two appropriate components, such as a hydrocarbon in an aliphatic or aromatic liquid diluent to form a paste. Alternatively, the activating solution can be added to a fluidized or stirred bed comprising particles of supported metal complex, activated in an amount less than the amount that causes paste formation, desirably an amount approximately equal to the total pore volume of the support. In another embodiment, the metal complex is activated

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39/49 first through contact with the activating compound to form a solution and the solution is added to the functionalized support using any amount of solution. The temperature, pressure, and contact time for this treatment are not critical, they can generally range from -20 ^o C to 150 ^o C, from 1 Pa to 10,000 MPa, more preferably at atmospheric pressure (100 kPa) for 5 minutes at 48 hours.

[127] Before using the supported catalyst of the invention, the residual diluent or solvent, if any, can be removed to obtain a free flowing powder. This is preferably done by applying a technique that only removes the liquid and maintains the resulting solid, such as by applying heat, reduced pressure, drying, evaporation or a combination thereof. Alternatively, a suspension or dispersion of the supported catalyst is a non-solvent, such as mineral oil, hydrogenated diesel fuel, kerosene, or other hydrocarbon liquid can also be prepared, especially for use in a paste polymerization. All steps of the present process must be carried out in the absence of oxygen and moisture. The resulting supported catalyst can be stored and shipped under inert conditions or used substantially simultaneously with its manufacture.

[128] The activated supported metal complexes of the present invention can be used in addition to the polymerization processes, where one or more addition-curable monomers are contacted with the supported catalyst of the invention, under conditions of addition polymerization. Gaseous or pasty polymerization conditions can be employed, or a combination of such conditions

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40/49 in multiple reactors.

Suitable addition polymerizable monomers include ethylenically unsaturated monomers, acetylenic compounds, conjugated or unconjugated dienes, polyenes. Preferred monomers include olefins and diolefins for example, alpha-olefins having to

20,000, preferably from to 20, more preferably from 2 to carbon atoms, combinations of two or more of such alphaolefins, and other combinations with one or more conjugated or unconjugated C4-20 dienes. Especially suitable alpha-olefins include, for example, ethylene, propylene,

1butene, 1-pentene, 4-methyl-1-pentene, 1-hexene,

1-heptene,

1octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,

1tridecene, 1-tetradecene, 1-pentadecene, or combinations thereof, as well as oligomeric or polymeric reaction products with long chain vinyl terminations formed during polymerization, and C4-10 dienes, including 1,4-butadiene, 1,4hexadiene, and ethylidenonorbornene. Preferably, the alphaolefins are ethylene, propene, 1-butene, 4-methyl-pentene-1, 1-hexene, 1-octene, and combinations of ethylene and / or propene with one or more of these other alpha-olefins. Other preferred monomers include styrene, halo or alkyl substituted styrenes, tetrafluoroethylene, vinylcyclobutene, 1,4hexadiene, dicyclopentadiene, ethylidene norbornene, and 1,7octadiene. Mixtures of the aforementioned monomers can also be employed.

[130] The supported catalyst compositions can be formed in situ in the polymerization mixture by introducing into said mixture an inactivated supported metal complex of the present invention and an appropriate cocatalyst,

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41/49 preferably an activating cocatalyst for cation formation, together with other components of the polymerization, including reagents, solvents or olefinic diluents. Preferably, however, the metal complex containing one or more binders linked to ortho-metal and an activating cocatalyst are preferably combined in an appropriate solvent or diluent, followed by combination with the ethylenically or polyethylene functionalized particulate solid support and the resulting supported catalyst composition is added to the polymerization mixture, with or without intermediate recovery of the supported catalyst composition.

[131] The supported catalyst composition can be advantageously employed in a polymerization process in solution, paste or gas phase, under high pressure. A high pressure process is generally carried out at temperatures ranging from 100 to 400 ^o C and at pressures above 50.0 MPa. A paste process typically uses an inert hydrocarbon diluent and temperatures from 0 ^o C to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium. Preferred temperatures range from 40 ^o C to 115 ^o C. The solution process is carried out at temperatures ranging from the temperature at which the resulting polymer is soluble in an inert solvent to 275 ^o C, preferably at temperatures from 130 ^o C to 260 ^o C, more preferably from 150 ^o C to

240 ^o C. Preferred inert solvents are C1-20 hydrocarbons and preferably C5-10 aliphatic hydrocarbons, including mixtures thereof.

Solution and paste processes are generally carried out under pressure between

100 kPa a

MPa.

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42/49

Typical operating conditions are generally conducted at pressures between 100 kPa to 10 MPa. Typical operating conditions for gas phase polymerizations are 20 to 100 ^o C, more preferably 40 to 80 ^o C. In gas phase processes the pressure is typically 10 kPa to 10 MPa. Condensed monomer or diluent can be injected into the reactor to aid in heat removal through latent vaporization heat.

[132] Preferably for use in gas phase polymerization processes, the support has an average particle diameter of 20 to 200 mm, more preferably from 30 to 150 qm, and most preferably from 50 mm to 100 m. Preferably for use in paste polymerization processes, the support has an average particle diameter of 1 to 200mm, more preferably 5mm to 100mm and most preferably 20mm to 80mm. Preferably for use in solution polymerization processes and under high pressure, the support has an average particle diameter of 1 to 40 mm, more preferably 1 mm to 30 mm, and most preferably 1 mm to 20 mm.

[133] In the polymerization process of the present invention, molecular weight control agents, chain transfer agents and / or chain transfer agents can also be employed. Examples of such agents include hydrogen, organometallic compounds such as trialkyl aluminum or dialkylzinc compounds and other known compounds. The use of chain transfer agents for the preparation of segmented polymers has been previously described in WO2005 / 09425, WO2005 / 09426 and WO2005 / 09427, among other descriptions.

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43/49

Specific Embodiments [134] The specific embodiments of the invention described below and their combinations are especially desirable and cited herein to provide a detailed description of the appended claims.

1. Supported metal complex, comprising the reaction product of:

a transition metal complex of a polyvalent heteroaryl donor binder containing at least one ortho-metallized aromatic binder group, and an ethylenically or poly (ethylenically) functionalized organic or inorganic solid.

2. Complex, according to embodiment 1, where the particulate solid is modified silica by reaction with a trialkylaluminium compound and further functionalized by reaction with an ethylenically unsaturated compound containing protonated Lewis base functionality.

3. Complex according to embodiment 2, the ethylenically unsaturated compound containing protonated Lewis base functionality being a functionalized compound of hydroxyl, thiol, amine or phosphine containing vinyl functionality.

4. Complex, according to embodiment 2, with the ethylenically unsaturated compound containing protonated Lewis base functionality being a primary ethylenically or polyethylenically unsaturated aliphatic compound of alcohol, thiol, amine or phosphine containing from 3 to 20 carbons.

5. Complex, according to embodiment 1, where the metal complex is a cationic complex or is activated for polymerization of olefins by combining with a

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44/49 cocatalyst before combining with the particulate solid.

6. Complex, according to embodiment 1, the metal complex being a group 4 metal complex.

7. Complex according to embodiment 3, the metal complex being [[2,6-bis (1-methylethyl) phenyl] -a- [2- (1 methylethyl) phenyl] -6- (1,2- naphthalendiil-KC ² ) -2pyridinomethanaminate (2 -) - KN, kN] methyl hafnium] ⁺ [methyl tris (pentafluorophenyl) borate] ^- .

8. Supported metal complex, useful for the polymerization by addition of addition polymerizable monomers, said composition comprising a transition metal complex of a polyvalent heteroaryl donor binder, and a functionalized particulate organic or inorganic solid, the metal complex being transition phase is covalently bonded to the particulate solid by adding functional ethylene groups from the solid to one or more ortho-metal-aryl bonds of the transition metal complex.

9. Complex, according to embodiment 8, with the particulate solid being modified silica by reaction with a trialkylaluminum compound and further functionalized by reaction with an ethylenically unsaturated compound containing protonated Lewis base functionality.

10. Complex according to embodiment 9, with the ethylenically unsaturated compound containing Lewis base functionality being a functionalized hydroxyl, thiol, amine or phosphine compound containing vinyl functionality.

11. Complex according to embodiment 9, the ethylenically unsaturated compound containing Lewis base functionality being a primary aliphatic ethylenically or polyethylene unsaturated alcohol, amine, thiol or

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45/49 phosphine containing 3 to 20 carbons.

12. Complex, according to embodiment 8, where the metal complex is a cationic complex or is activated for polymerization of olefins through combination with a cocatalyst.

13. Complex, according to embodiment 12, the metal complex being a group 4 metal complex.

14. Complex according to embodiment 12, the metal complex being [[2,6-bis (1-methylethyl) phenyl] -a- [2- (1 methylethyl) phenyl] -6- (1,2- naphthalendiil-KC ² ) -2pyridinomethanaminate (2 -) - KN, kN] methyl hafnium] ⁺ [methyl tris (pentafluorophenyl) borate] ^- .

15. A process for preparing a support, comprising pendant ethylenically saturated functional groups, comprising combining an inorganic oxide material comprising surface hydroxyl groups functionalized with Lewis acid with an ethylenically unsaturated aliphatic compound, functionalized with protonated Lewis base.

16. Process for preparing a support, containing pendant groups with vinyl functionality, comprising combining an inorganic oxide material containing surface hydroxyl groups functionalized with Lewis acid with an aliphatic vinyl compound substituted with hydroxyl, thiol, alkylamino, di (alkyl) amino, alkylphosphine, or di (alkyl) phosphine.

17. Process, according to embodiment 15, with the vinyl aliphatic compound being a primary aliphatic alcohol substituted with vinyl having from 6 to 20 carbons.

18. Addition polymerization process, comprising contacting one or more addition-curable monomers under

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46/49 polymerization conditions by addition with a supported catalytic composition, as defined in any of embodiments 1-14, or preparable, as defined in any of embodiments 15-17.

[135] Having described the invention, the following examples are provided as a complementary illustration of the invention and should not be construed as restrictive. Unless otherwise stated, all parts and percentages are by weight. The apparent density of the polymers produced was determined according to ASTM 1895.

EXAMPLES [136] Silica modified with tri (ethyl) aluminum - Support A ((C ₂ H5) Al-O-Silica) [137] In a glove chamber under an inert atmosphere, 6.00g of silica with a numerical average particle size of 25 pm (ES757 ^TM from Ineos Corporation) calcined in air at 200 ^o C for 12 hours is added to a 100 ml glass vial and converted into a paste with 30 ml of toluene. To the stirred paste, 12.0 ml of a 1M solution of triethyl aluminum in hexanes was added dropwise. The mixture is stirred on a mechanical stirrer for 4 hours. The resulting solids are collected in a frit funnel, washed twice with 30 ml of toluene, and dried under reduced pressure for 16 hours.

[138] Example 1 - Silica modified with V- undecenyloxy (ethyl) aluminum (CH2 = CH2- (C9H18) -O-Al (C2H5) -OSilica) (vinyl functionalized support according to the present invention) [139] Glove chamber under inert atmosphere, 4.00 g of Support A is added to a 100 ml glass vial and converted into a paste with 20 ml of toluene. To the folder under

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47/49 stirring 0.16 ml (200 pm) of alcohol was added dropwise

V-undecenyl. The mixture is stirred on a mechanical stirrer for 2 hours. The resulting solids are collected in a frit funnel, washed twice with 20 ml of toluene, and dried under reduced pressure for 16 hours.

Catalyst A (comparative).

[140] In a glove chamber under an inert atmosphere, 1.00 g of Support A is added to a 20 ml glass vial and converted into paste with 5 ml of toluene. To the stirred paste was added dropwise 7.5 ml of a 0.04M solution of tris (pentafluorophenyl) boron in toluene. Then, 2.5ml of a 0.04M solution of dimethyl [N- [2,6-bis (1-methylethyl) phenyl] to [2- (1-methylethyl) phenyl] -6- (1,2-naphthalendiil -KC ² ) -2pyridinomethanaminate (2) -KN, kN] hafnium, prepared according to US-A-2004/0220050, is diluted with 5ml of additional toluene and added to the paste, thus forming the active catalytic species, which is believed be [141] [tris (pentafluorophenyl) methylborate] ^- de [[2,6bis (1-methylethyl) phenyl] a- [2- (1-methylethyl) phenyl] -6- (1,2naphthalendiil-KC) -2- pyridinomethanaminate (2) -KN, kN] methyl hafnium] ⁺ . The mixture is stirred on a mechanical stirrer for 2 hours. The resulting solids are collected in a frit funnel, washed twice with 10 ml of toluene and dried under reduced pressure for 16 hours.

[142] Example 2 (Supported Catalyst according to the invention) [143] In a glove chamber under an inert atmosphere, 1.00 g of support B (Example 1) is added to a 20 ml glass vial and converted into a paste with 5ml of toluene. To the paste under agitation, 7.5 ml of a solution was added dropwise

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0.04M tris (pentafluorophenyl) boron in toluene. Then, 2.5 ml of a 0.04M solution of [144] dimethyl [N- [2,6-bis (1-methylethyl) phenyl] oc- [2- (1-methylethyl) phenyl] -6- ( 1,2-naphthalendiil-KC ² ) -2pyridinomethanaminate (2) -kN ¹ , kN ² ] hafnium are diluted with 5ml of additional toluene and added to the paste. The mixture is stirred on a mechanical stirrer for 2 hours. The resulting solids are collected in a frit funnel, washed twice

times with 10 ml of toluene, and dried under pressure reduced for 16 hours. [145] The aforementioned preparation on one complex activated metallic, switched on and supported is illustrated schematically in Following diagram:

+ (CH,) _g CH = CH ₂ /

O ^X A1 (C ₂ H ₅ ) z

O

Conducted Paste Polymerization [146] in Reactor of

Batch [147]

A clean, purged 2 liter autoclave reactor

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49/49 with nitrogen, jacketed and stirred is loaded with 0.5 g of silica sweeper modified with triethyl aluminum (Support A), followed by 600 sccm of H ₂ and 680 g of propylene. The mixture is stirred for 5 minutes and then heated to 70 ^o C. The supported catalyst (0.25 g converted into a paste with 10 ml of hexane) is added through nitrogen pressure. After 40 minutes of polymerization, the reactor is discharged and cooled and the resulting polymer (if any) is removed from the reactor. The results are shown in Table 1.

Table 1

Operation Catalyst Support Efficiency (kg / g Hf) 1* THE* THE 0 2 Example 2 Example 1 1308

* comparative, not an example of the invention [148] The lack of polymerization activity in the comparative catalyst demonstrates that the efficient bonding of the metal complex to the silica surface is conducted according to the invention due, it is believed, to the insertion of the unsaturated vinyl functionality bonded to silica in the available ortho-metallic functionality of the metal complex, without loss of active catalytic species (which is assumed to be a cationic complex) or leaching of the activated metal complex of the silica, under conditions of paste polymerization.

Claims (8)

1. Supported metal complex, characterized by the fact that it comprises the reaction product of: (A) a transition metal complex of a polyvalent heteroaryl donor binder containing at least one ortho-metallized aromatic binder group, and (B) an ethylenically or poly (ethylenically) functionalized organic or inorganic solid. 2. Complex, according to claim 1, characterized by the fact that the particulate solid is modified silica by reaction with a trialkylaluminium compound and further functionalized by reaction with an ethylenically unsaturated compound containing protonated Lewis base functionality. 3. Complex according to claim 2, characterized in that the ethylenically unsaturated compound containing protonated Lewis base functionality is a functionalized compound of hydroxyl, thiol, amine or phosphine containing vinyl functionality. 4. Complex according to claim 1, characterized in that the complex is a cationic complex or is activated by polymerization of olefins by combining with a cocatalyst before combining with the particulate solid. 5. Complex according to claim 2, characterized in that the ethylenically unsaturated compound containing Lewis base functionality is a primary aliphatic ethylenically or polyethylenically unsaturated alcohol, amine, thiol or phosphine containing 3 to 20 carbons. 6. Complex according to claim 1, characterized Petition 870180145510, of 10/29/2018, p. 55/57 2/2 because it is a group 4 metal complex. 7. Complex according to claim 3, characterized in that it is [[2,6-bis (1-methylethyl) phenyl] -a- [2- (1methylethyl) phenyl] -6- (1,2-naphthalendiil -KC) -2-pyridinomethanaminate (2 -) - KN, kN] methyl hafnium] [methyl tris (pentafluorophenyl) borate] ^- . 8. Addition polymerization process, characterized in that it comprises contacting one or more addition polymerizable monomers under addition polymerization conditions with a supported catalytic composition, as defined in any of claims 1-7.